EP1479744A1 - Adhésifs de contact comprenant des polymères et des composés de silicium - Google Patents

Adhésifs de contact comprenant des polymères et des composés de silicium Download PDF

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Publication number
EP1479744A1
EP1479744A1 EP04008707A EP04008707A EP1479744A1 EP 1479744 A1 EP1479744 A1 EP 1479744A1 EP 04008707 A EP04008707 A EP 04008707A EP 04008707 A EP04008707 A EP 04008707A EP 1479744 A1 EP1479744 A1 EP 1479744A1
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EP
European Patent Office
Prior art keywords
pressure
sensitive adhesive
polymer
adhesive according
silicon compounds
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EP04008707A
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German (de)
English (en)
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EP1479744B1 (fr
Inventor
Oral Dr. Aydin
Andree Dragon
Heiko Diehl
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BASF SE
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BASF SE
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/54—Inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/02—Polysilicates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2852—Adhesive compositions
    • Y10T428/2878—Adhesive compositions including addition polymer from unsaturated monomer
    • Y10T428/2891—Adhesive compositions including addition polymer from unsaturated monomer including addition polymer from alpha-beta unsaturated carboxylic acid [e.g., acrylic acid, methacrylic acid, etc.] Or derivative thereof

Definitions

  • the invention relates to a pressure-sensitive adhesive containing an aqueous dispersion of a Polymers, characterized in that the dispersion in addition to the polymer Silicon compounds selected from polymeric silicates, water-soluble alkali silicates (Water glass), silanes and silanes obtained by condensation Contains silicones
  • silica is to be radiation-crosslinkable Known polymers.
  • the object of the present invention was to improve the adhesion of the pressure-sensitive adhesives without loss of cohesion.
  • these advantageous properties also be achieved with bonds on non-polar surfaces.
  • the pressure-sensitive adhesive contains an aqueous polymer dispersion.
  • the in the aqueous dispersion dispersed polymer is preferably by radical polymerization of ethylenically unsaturated compounds (monomers) available.
  • the polymer is preferably at least 40% by weight, preferably at least 60 wt .-%, more preferably at least 80 wt .-% of so-called Principal monomers.
  • the main monomers are selected from C 1 -C 20 -alkyl (meth) acrylates, vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinylaromatics having up to 20 carbon atoms, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers of from 1 to 10 carbon atoms. Atoms containing alcohols, aliphatic hydrocarbons having 2 to 8 carbon atoms and one or two double bonds or mixtures of these monomers.
  • Examples include (meth) acrylic acid alkyl esters having a C 1 -C 10 alkyl radical, such as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate and 2-ethylhexyl acrylate.
  • mixtures of (meth) acrylic acid alkyl esters are also suitable.
  • Vinyl esters of carboxylic acids having 1 to 20 carbon atoms are e.g. Vinyl laurate, stearate, Vinyl propionate, vinyl versatate and vinyl acetate.
  • Vinyltaromatic compounds include vinyltoluene, a- and p-methylstyrene, a-butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene.
  • nitriles are acrylonitrile and methacrylonitrile.
  • the vinyl halides are ethylenically unsaturated substituted with chlorine, fluorine or bromine Compounds, preferably vinyl chloride and vinylidene chloride.
  • vinyl ethers there are e.g. Vinyl methyl ether or vinyl isobutyl ether.
  • hydrocarbons having 2 to 8 carbon atoms and one or two olefinic double bonds are ethylene, propylene, butadiene, isoprene and chloroprene called.
  • Preferred main monomers are the C 1 - to C 10 -alkyl acrylates and -methacrylates, in particular C 1 - to C 8 -alkyl acrylates and -methacrylates and vinylaromatics, in particular styrene and mixtures thereof.
  • methyl acrylate methyl methacrylate, ethyl acrylate, n-butyl acrylate, n-hexyl acrylate, octyl acrylate and 2-ethylhexyl acrylate, styrene and Mixtures of these monomers.
  • the polymer may contain other monomers, e.g. Monomers with carboxylic acid, sulfonic acid or phosphonic acid groups.
  • monomers are, for example, hydroxyl-containing monomers, in particular C 1 -C 10 -hydroxyalkyl (meth) acrylates, (meth) acrylamide.
  • Phenyloxyethylglycol mono (meth) acrylate may be mentioned as further monomers.
  • the polymer is at least 40 wt .-%, in particular at least 60 wt .-% and most preferably at least 80 wt .-% of C 1 -C 20 -, in particular C 1 -C 10 alkyl (meth) acrylates ,
  • Emulsion polymerization it is therefore an emulsion polymer.
  • the preparation may be e.g. also by solution polymerization and subsequent Dispersion in water.
  • ionic and / or nonionic emulsifiers and / or protective colloids or stabilizers as surface-active compounds used.
  • Suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular substances, Georg-Thieme-Verlag, Stuttgart, 1961, pp. 411 to 420.
  • Suitable emulsifiers are both anionic, cationic and nonionic emulsifiers into consideration.
  • Preferably used as accompanying surface-active substances are exclusively emulsifiers whose molecular weight, in contrast to the protective colloids, is usually below 2000 g / mol.
  • the individual components must be compatible with each other, which can be checked in case of doubt by hand on fewer preliminary tests.
  • anionic and nonionic emulsifiers are used as surface-active substances.
  • Common accompanying emulsifiers are, for example, ethoxylated fatty alcohols (EO degree: 3 to 50, alkyl radical: C 8 - to C 36 ), ethoxylated mono-, di- and tri-alkylphenols (EO degree: 3 to 50, alkyl radical: C 4 - to C 9 ), alkali metal salts of dialkyl esters of sulfosuccinic acid and alkali metal and ammonium salts of alkyl sulfates (alkyl radical: C 8 - to C 12 ), of ethoxylated alkanols (EO degree: 4 to 30, alkyl radical: C 12 - to C 18 ), of ethoxylated alkylphenols (EO degree: 3 to 50, alkyl radical: C 4 - to C 9 ), of alkylsulfonic acids (alkyl radical: C 12 -
  • R 5 and R 6 are hydrogen or C 4 - to C 14 -alkyl and are not simultaneously hydrogen
  • X and Y may be alkali metal ions and / or ammonium ions.
  • R 5 , R 6 are linear or branched alkyl radicals having 6 to 18 C atoms or hydrogen and in particular having 6, 12 and 16 C atoms, wherein R 5 and R 6 are not both simultaneously hydrogen.
  • X and Y are preferably sodium, potassium or ammonium ions, with sodium being particularly preferred.
  • Particularly advantageous are compounds II in which X and Y are sodium, R 5 is a branched alkyl radical having 12 C atoms and R 6 is hydrogen or R 5 .
  • technical mixtures are used which have a proportion of 50 to 90% by weight of the monoalkylated product, for example Dowfax® 2A1 (trademark of the Dow Chemical Company).
  • Suitable emulsifiers are also found in Houben-Weyl, methods of organic Chemie, Volume 14/1, Macromolecular Materials, Georg Thieme Verlag, Stuttgart, 1961, Pages 192 to 208.
  • emulsifiers are e.g. Dowfax® 2 A1, Emulan® NP 50, Dextrol® OC 50, Emulsifier 825, Emulsifier 825 S, Emulan® OG, Texapon® NSO, Nekanil® 904 S, Lumiten® I-RA, Lumiten E 3065, Disponil FES 77, Lutensol AT 18, Steinapol VSL, Emulphor NPS 25.
  • the surfactant is usually used in amounts of from 0.1 to 10% by weight, based on the monomers to be polymerized.
  • Water-soluble initiators for emulsion polymerization are e.g. Ammonium and Alkali metal salts of peroxodisulfuric acid, e.g. Sodium peroxodisulfate, hydrogen peroxide or organic peroxides, e.g. tert-butyl hydroperoxide.
  • peroxodisulfuric acid e.g. Sodium peroxodisulfate
  • hydrogen peroxide or organic peroxides e.g. tert-butyl hydroperoxide.
  • red-ox reduction-oxidation
  • the red-ox initiator systems consist of at least one mostly inorganic one Reducing agent and an inorganic or organic oxidizing agent.
  • the oxidation component is e.g. to those already mentioned above Initiators for emulsion polymerization.
  • the reducing component is e.g. Alkali metal salts of sulfuric Acid, e.g. Sodium sulfite, Sodium hydrogen sulfite, Alkaline salts of Dischwefligen Acid such as sodium disulfite, bisulfite addition compounds of aliphatic aldehydes and ketones such as acetone bisulfite or reducing agents such as hydroxymethanesulfinic acid and their salts, or ascorbic acid.
  • the red-ox initiator systems can be used under Co-use of soluble metal compounds whose metallic component in several Validity levels can occur.
  • Typical redox initiator systems are e.g. Ascorbic acid / iron (II) sulfate / sodium peroxodisulfate, tert-butyl hydroperoxide / sodium disulfite, tert-butyl hydroperoxide / Na-hydroxymethanesulfinic acid.
  • the individual components, e.g. the reducing component may also be mixtures e.g. a mix of the sodium salt of hydroxymethanesulfinic acid and sodium disulfite.
  • the compounds mentioned are mostly used in the form of aqueous solutions, the lower concentration being the amount of water acceptable in the dispersion and the upper concentration by the solubility of the compound in question Water is determined.
  • the concentration is 0.1 to 30 wt .-%, preferably 0.5 to 20 wt .-%, particularly preferably 1.0 to 10 wt .-%, based on the solution.
  • the amount of initiators is generally 0.1 to 10 wt .-%, preferably 0.5 to 5 wt .-%, based on the monomers to be polymerized. There can also be several, find various initiators in the emulsion polymerization use.
  • regulators may be used, e.g. in amounts from 0 to 0.8 Parts by weight, based on 100 parts by weight of the monomers to be polymerized by the molecular weight is reduced.
  • Suitable are e.g. Compounds with a thiol group such as tert-butylmercaptan, thioglycolic acid ethylacrylic ester, mercaptoethynol, Mercaptopropyltrimethoxysilane or tert-dodecylmercaptan.
  • the emulsion polymerization is carried out usually at 30 to 130, preferably 50 to 90 ° C.
  • the polymerization medium may consist of both water and mixtures consist of water and thus miscible liquids such as methanol. Preferably, only water is used.
  • the emulsion polymerization can be both as a batch process as well as in the form of a feed process, including staged or Gradientenfahrweise be performed.
  • a polymer seed can be provided.
  • the way in which the initiator in the course of radical aqueous emulsion polymerization is added to the polymerization vessel the average person skilled in the art known. It can be both completely charged into the polymerization vessel, as well as according to its consumption in the course of the radical aqueous Emulsion polymerization are used continuously or stepwise. In detail this depends on the chemical nature of the initiator system as well as on the polymerization temperature from. Preferably, a part is presented and the rest after Given the consumption of the polymerization zone.
  • the individual components can the reactor in the feed process from above, in be added to the side or from below through the reactor bottom.
  • aqueous dispersions of the polymer in the Usually with solids contents of 15 to 75 wt .-%, preferably from 40 to 75 wt .-% receive.
  • the polymer thus prepared is preferably in the form of its aqueous dispersion used.
  • the glass transition temperature of the polymer or of the emulsion polymer is preferably -60 to 0 ° C, more preferably -60 to -10 ° C and most especially preferably -60 to -20 ° C.
  • the glass transition temperature can be determined by conventional methods such as differential thermal analysis or Differential Scanning Calorimetry (see, e.g., ASTM 3418/82, so-called "midpoint temperature ").
  • the aqueous polymer dispersion contains silicon compounds selected from polymeric silicates, water-soluble alkali silicates, silanes and from the Silanes obtainable by condensation Silokonen.
  • the polymeric silicates are, in particular, polymeric silicon dioxide as by condensation of silica or preferably water-soluble alkali metal silicates (Water glass) is available.
  • the water-soluble alkali silicates may be e.g. to aqueous solutions of Alkali silicates, e.g. around potash water glass (obtainable by dissolving a melt Quartz sand with (potash) or soda waterglass (available by dissolving a Melt of quartz sand and soda) act.
  • potash water glass obtainable by dissolving a melt Quartz sand with (potash) or soda waterglass (available by dissolving a Melt of quartz sand and soda) act.
  • the silanes are silicon compounds with organic substituents on the silicon atom.
  • silanes which can condense to form silicones and, in particular, to this have one or more alkoxy groups as a substituent on the silicon atom.
  • silanes having a molecular weight of less than 2000 g / mol, in particular less than 1000 g / mol.
  • the alkoxy group very particularly preferably is the methoxy group or ethoxy group into consideration.
  • the remaining groups represent another organic radical, in particular an organic radical which may contain up to 20 carbon atoms and optionally heteroatom, such as O, N, S.
  • organic radical which may contain up to 20 carbon atoms and optionally heteroatom, such as O, N, S.
  • Particularly suitable are alkyl groups, in particular C 1 -C 20 , C 1 -C 10 -alkyl groups.
  • the silane contains in addition to the alkoxy group at least one further hydrophilic group selected from hydroxy, epoxy, Carboxy, mercapto and amino groups.
  • the silanes contain next Alkoxy groups one to four, in particular one or two of said hydrophilic Groups.
  • amino groups in particular primary or secondary amino groups, more preferably primary amino groups (-NH 2 ).
  • the further hydrophilic groups are preferably bonded to the organic radicals R 1 -R 4 .
  • these are alkyl groups which are substituted by the hydrophilic group.
  • Suitable compounds are e.g. Mono-, di- or Trialkoxysilane, wherein it is at the remaining radicals are organic groups, in particular alkyl groups, of at least one by one or more, e.g. substituted two hydrophilic groups is.
  • silicones which are obtained by condensation of silanes, in particular the above silanes are available.
  • Preferred silicon compounds are the water-soluble alkali silicates and the Silanes with other hydrophilic groups.
  • silanes with further hydrophilic groups are particularly preferred.
  • the content of the silicon compounds is preferably at least 0.0001 in particular at least 0.05, very particularly preferably at least 0.1 or at least 0.5 parts by weight; the content of silicon compounds is preferably not more than 10 parts by weight, more preferably not more than 5 parts by weight, very particularly preferably a maximum of 3 parts by weight, based in each case on 100% by weight of the dispersion dispersed polymers.
  • the silicon compounds can be added to the aqueous polymer dispersion at any time become. Basically, they can also be used before or during the polymerization the monomers are present, but is preferred after the completion of the Polymerization.
  • the silicon compounds are first in Water predispersed and the resulting dispersion of the silicon compounds is then added to the polymer dispersion.
  • the silicon compounds in the polymer dispersion ultimately as discrete particles, in particular with a particle diameter of 5 to 200 nm, preferably from 5 to 100 nm.
  • the pressure-sensitive adhesive may contain, in addition to the aqueous dispersion of the polymer, further additives contain.
  • the aqueous dispersion may e.g. a tackifier, i. a tackifying Resin, to be added. Tackifiers are e.g. from Adhesive Age, July 1987, Page 19-23 or polym. Mater. Sci. Closely. 61 (1989), pages 588-592.
  • Tackifiers are e.g. Natural resins, such as rosins and their disproportionation or isomerization, polymerization, dimerization, hydrogenation Derivatives. These may be in their salt form (with, for example, monovalent or polyvalent counterions (Cations) or preferably in their esterified form. Alcohols used for esterification may be mono- or polyvalent. Examples are methanol, Ethanediol, diethylene glycol, triethylene glycol, 1,2,3-propanethiol, pentaerythritol.
  • hydrocarbon resins e.g. Coumarone-indene resins, polyterpene resins, Hydrocarbon resins based on unsaturated CH compounds, such as Butadiene, pentene, methylbutene, isoprene, piperylene, divinylmethane, pentadiene, cyclopentene, Cyclopentadiene, cyclohexadiene, styrene, ⁇ -methylstyrene, vinyltoluene use.
  • unsaturated CH compounds such as Butadiene, pentene, methylbutene, isoprene, piperylene, divinylmethane, pentadiene, cyclopentene, Cyclopentadiene, cyclohexadiene, styrene, ⁇ -methylstyrene, vinyltoluene use.
  • tackifiers are increasingly also polyacrylates, which have a low molecular weight used.
  • these polyacrylates have a weight-average molecular weight M w below 30,000.
  • the polyacrylates are preferably at least 60, in particular at least 80 wt .-% of C 1 -C 8 alkyl (meth) acrylates.
  • Preferred tackifiers are natural or chemically modified rosin resins. Rosin resins consist predominantly of abietic acid or abietic acid derivatives.
  • the tackifiers can be preferred in a simple manner to the polymers according to the invention be added to the aqueous dispersions of the polymers.
  • the amount by weight of the tackifiers is preferably 5 to 100 parts by weight. especially preferably 10 to 50 parts by weight. based on 100 parts by weight of polymer. (Solid / solid).
  • tackifiers e.g. still other additives e.g. Thickener, preferably Associative thickeners, defoamers, plasticisers, pigments, wetting agents or Find fillers when used as a pressure-sensitive adhesive.
  • the invention Pressure-sensitive adhesives therefore contain, in addition to the aqueous polymer dispersion, if appropriate still tackifier and / or the above additives.
  • the pressure-sensitive adhesives in particular Wetting aid e.g. Fatty alcohol ethoxylates, alkylphenol ethoxylates, sulfosuccinic acid esters, Nonylphenol ethoxylates, polyoxyethylenes / -propylenes or sodium dodecylsulfonates contain.
  • the amount is generally 0.05 to 5 parts by weight, in particular 0.1 to 3 parts by weight per 100 parts by weight of polymer (solid).
  • the pressure-sensitive adhesives are suitable for the production of self-adhesive articles, such as labels, Foils or adhesive tapes.
  • the pressure-sensitive adhesive can be prepared by conventional methods, e.g. by Rolling, knife-coating, brushing, etc. onto supports, e.g. Paper or polymer films, preferred consisting of polyethylene, polypropylene, which may be stretched biaxially or monoaxially can, polyethylene terephthalate, polyvinyl chloride, polystyrene, polyamide or metal applied become.
  • carriers with non-polar surfaces e.g. from polyolefins, in particular polyethylene or polypropylene, since the inventive Dispersions adhere well.
  • the water may preferably be by drying be removed at 50 to 150 ° C.
  • the carriers may be before or after application of the adhesive to tapes, labels or films are cut. to later use, the pressure-sensitive adhesive coated side of the substrates, with a release paper, e.g. covered with a siliconised paper.
  • the self-adhesive articles according to the invention have very good adhesive properties, in particular a good adhesion to the substrates and a high cohesion (internal Strength in the adhesive layer). These good qualities are also achieved if the dispersions or pressure-sensitive adhesives contain wetting aids. They have also a good adhesion to non-polar surfaces and are therefore particularly suitable for substrates with non-polar surfaces, e.g. Polyolefin surfaces, e.g. polyethylene (HDPE or LDPE) or polypropylene.
  • non-polar surfaces e.g. Polyolefin surfaces, e.g. polyethylene (HDPE or LDPE) or polypropylene.
  • the pressure-sensitive adhesive also does not tend to rewind, i. he remains on the carrier after stripping off e.g. of the label.
  • the self-adhesive articles also have a high water resistance.
  • Lumiten® I-SC and potassium silicate or a silane were added to the Acronal® A 220 in the added in the tables.
  • the weights are wt. Parts, based on 100 parts by weight of polymer.
  • the pressure-sensitive adhesives were coated with an amount of 19 gypsum 18 g / m 2 on polyethylene film or paper as support and dried at 90 ° C. for 3 minutes.
  • the pressure-sensitive adhesive coated carrier was cut into 25 mm wide test strips. To determine the shear strength, the test strips were glued with a Surface of 12.5 x 12.5 mm on steel, or with a glued surface of 25 x 25 mm Glued on glass, rolled 1 time with a 1-kg roll, stored 10 minutes (im Standard climate, 50% rel. Humidity 1 bar, 23 ° C) and then hanging with a 1 kg or 1.5 kg weight (in standard climate). The measure of the shear strength was the time in hours until the weight dropped; it was the respectively Average calculated from 5 measurements.
  • the peel strength was determined 24 hours after the bonding. After this time the adhesive power has fully developed.
  • the test methods essentially correspond to the Finat test methods (FTM) No. 1 and No. 8.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Paints Or Removers (AREA)
EP04008707A 2003-05-20 2004-04-13 Adhésifs de contact comprenant des polymères et des composés de silicium Expired - Lifetime EP1479744B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10323048 2003-05-20
DE10323048A DE10323048A1 (de) 2003-05-20 2003-05-20 Haftklebstoffe, enthaltend Polyethylen

Publications (2)

Publication Number Publication Date
EP1479744A1 true EP1479744A1 (fr) 2004-11-24
EP1479744B1 EP1479744B1 (fr) 2007-08-01

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EP04008707A Expired - Lifetime EP1479744B1 (fr) 2003-05-20 2004-04-13 Adhésifs de contact comprenant des polymères et des composés de silicium

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US (1) US7041720B2 (fr)
EP (1) EP1479744B1 (fr)
AT (1) ATE368713T1 (fr)
DE (2) DE10323048A1 (fr)
ES (1) ES2287604T3 (fr)

Cited By (3)

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WO2008019963A1 (fr) * 2006-08-14 2008-02-21 Basf Se Masses à enduire le papier contenant des silicasols
DE102007021776A1 (de) 2007-05-10 2008-11-13 Lohmann Gmbh & Co Kg Verfahren zur Herstellung anorganisch/organischer Hybridpolymere
US8123899B2 (en) 2006-07-12 2012-02-28 Basf Aktiengesellschaft Polyurethane adhesive with a silane compound as an additive

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* Cited by examiner, † Cited by third party
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US20090111929A1 (en) * 2006-04-28 2009-04-30 Basf Se Contact adhesive containing 2-ethylhexylacrylate and hydroxybutyl(meth) acrylate
JP2009535439A (ja) * 2006-04-28 2009-10-01 ビーエーエスエフ ソシエタス・ヨーロピア ｎ−ブチルアクリレートおよびヒドロキシブチル（メタ）アクリレートを含有する感圧接着剤
EP2038358B1 (fr) 2006-06-30 2012-12-26 Basf Se Film adhésif avec au moins deux phases continues
EP2084240B1 (fr) * 2006-10-23 2016-06-08 Basf Se Adhésif sensible à la pression contenant un acrylate d'alkyle en c10
US7754812B2 (en) * 2007-01-16 2010-07-13 Xerox Corporation Adhesion promoter
US8357763B2 (en) * 2007-05-02 2013-01-22 Xerox Corporation Adhesion promoter
DE102007032955A1 (de) * 2007-07-14 2009-01-15 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Gegenstand mit einer Klebschicht und Klebstoffzusammensetzung mit einstellbarer Trennkraft
JP2011127038A (ja) * 2009-12-18 2011-06-30 Nitto Denko Corp 水分散型粘着剤組成物および粘着シート
DE102011106759C5 (de) * 2011-07-05 2017-02-09 Khs Gmbh Verfahren zur Herstellung von Gebinden
WO2013004340A1 (fr) 2011-07-05 2013-01-10 Khs Gmbh Procédé de réalisation d'emballages multiples à partir de récipients
DE102011107265B4 (de) 2011-07-06 2023-06-01 Khs Gmbh Verfahren zur Herstellung von Gebinden
DE102011107264A1 (de) 2011-07-06 2013-01-10 Khs Gmbh Verfahren zur Herstellung von Gebinden
EP2855539B1 (fr) 2012-06-04 2018-04-25 Basf Se Adhésifs sensibles à la pression comprenant des résines acryliques portant une fonction acide de faible poids moléculaire et procédés de fabrication et d'utilisation correspondants
TWI521032B (zh) 2012-06-28 2016-02-11 羅門哈斯公司 濕性膠
DE102013106576A1 (de) 2013-06-24 2014-12-24 Coroplast Fritz Müller Gmbh & Co. Kg "Klebeband, insbesondere doppelseitiges Klebeband, und dessen Verwendung zum Bekleben unpolarer Oberflächen"
DE102013107574A1 (de) 2013-07-16 2015-01-22 Khs Gmbh Verfahren zur Herstellung von Gebinden
DE102015106665A1 (de) 2015-04-29 2016-11-03 Khs Gmbh Gebinde sowie Verfahren zur Herstellung eines solchen Gebindes

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000212527A (ja) * 1999-01-25 2000-08-02 Daicel Chem Ind Ltd シュリンクラベル
US6369153B1 (en) * 1995-10-25 2002-04-09 Rhodia Chimie Water-redispersible pulverulent composition of film-forming polymers prepared from ethylenically unsaturated monomers

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3314838A (en) * 1964-08-26 1967-04-18 Minnesota Mining & Mfg Pressure sensitive adhesives containing hollow spheroidal particles
DE2915887A1 (de) * 1979-04-19 1980-11-06 Wacker Chemie Gmbh Copolymerisate auf der basis von acrylestern, vinylacetat und aethylen
JP3819661B2 (ja) * 2000-02-24 2006-09-13 日東電工株式会社 感圧性接着シ―ト類および機能性フイルムの固定方法
DE10208843A1 (de) 2002-03-01 2003-09-11 Basf Ag UV-vernetzbare Schmelzhaftklebstoffe, enthaltend pyrogene Kieselsäuren

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6369153B1 (en) * 1995-10-25 2002-04-09 Rhodia Chimie Water-redispersible pulverulent composition of film-forming polymers prepared from ethylenically unsaturated monomers
JP2000212527A (ja) * 1999-01-25 2000-08-02 Daicel Chem Ind Ltd シュリンクラベル

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 200041, Derwent World Patents Index; Class A60, AN 1999-591297, XP002291701 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8123899B2 (en) 2006-07-12 2012-02-28 Basf Aktiengesellschaft Polyurethane adhesive with a silane compound as an additive
WO2008019963A1 (fr) * 2006-08-14 2008-02-21 Basf Se Masses à enduire le papier contenant des silicasols
DE102007021776A1 (de) 2007-05-10 2008-11-13 Lohmann Gmbh & Co Kg Verfahren zur Herstellung anorganisch/organischer Hybridpolymere

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EP1479744B1 (fr) 2007-08-01
US7041720B2 (en) 2006-05-09
DE502004004486D1 (de) 2007-09-13
DE10323048A1 (de) 2004-12-09
US20040235995A1 (en) 2004-11-25
ATE368713T1 (de) 2007-08-15

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